Nanostructured material and method of making the same

ABSTRACT

Nanostructured material exhibiting a random anisotropic nanostructured surface, and exhibiting an average reflection at 60 degrees off angle less than 1 percent. The nanostructured materials are useful, for example, for optical and optoelectronic devices, displays, solar, light sensors, eye wear, camera lens, and glazing.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of pending priorapplication Ser. No. 14/387,338, filed Sep. 23, 2014, which is aNational Stage Entry of PCT/US2013/027348, filed Feb. 22, 2013, whichclaims priority from U.S. Provisional Application 61/615,646, filed Mar.26, 2012, the disclosures of which are incorporated by reference intheir entireties herein.

BACKGROUND

When light travels from one medium to another, some portion of the lightis reflected from the interface between the two media. For example,typically about 4-5% of the light shining on a clear plastic substrateis reflected at the top surface.

The back lighting for mobile hand held and laptop devices are noteffective to provide desired display quality in the presence of thereflection of the external lighting from the top surface and internalinterfaces of the display devices, which in turn reduces contrast ratioand can downgrade viewing quality from the interfering image of externalobjects.

Different approaches have been employed to reduce the reflection of thetop surface of display devices. One approach is to use antireflectivecoatings such as multilayer reflective coatings consisting oftransparent thin film structures with alternating layers of contrastingrefractive index to reduce reflection. However, it can be difficult toachieve broadband antireflection using the multilayer antireflectivecoating technology.

Another approach involves using subwavelength surface structure (e.g.,subwavelength scale surface gratings) for broadband antireflection,where the phrase subwavelength is used to describe an object orstructure having one or more dimensions smaller than the length of thewave with which the object or structure interacts. For suppression ofFresnel reflections from optical surfaces, subwavelength structuredfeatures lead to continuous-profile surface-relief grating as aneffective medium to minimize reflection for a range of wavelengthsgreater than the subwavelength structured features on the surface.Methods for creating the subwavelength surface structure (e.g., bylithography) tend to be relatively complicated and expensive.

Reduction of reflection at broad angle is desired in applicationsrelated to optical and optoelectronic devices. It is difficult tofabricate deep surface structure providing low reflection (<1.5%) at 60degree off angle (i.e., 60 degree from normal to the surface) withtraditional subwavelength structure surface technology (e.g., bylithography). Micrometer-scale microstructures such as prism has beenintensively utilized to reduce reflection at broad angle for solarapplications, but this approach tends to result in high haze and is onlyapplicable when light is transporting from low refractive index mediumto high refractive index medium.

SUMMARY

In one aspect, the present disclosure describes a nanostructuredmaterial exhibiting a random anisotropic nanostructured surface, andexhibiting an average reflection at 60 degrees off angle less than 1percent (in some embodiments, less than 0.75, 0.5, 0.25, or less than0.2 percent). Typically, the nanostructured material comprises apolymeric matrix and a nanoscale dispersed phase.

In another aspect, the present disclosure describes a method of makingnanostructured materials described herein, the method comprising:

providing a polymeric matrix comprising a nanodispersed phase; and

anisotropically etching the polymeric matrix using plasma to form arandom anisotropic nanostructured surface.

In another aspect, the present disclosure describes a method of makingnanostructured materials described herein, the method comprising:

providing a polymeric matrix comprising a nanodispersed phase; and

etching at least a portion of the polymeric matrix using plasma to forma random anisotropic nanostructured surface.

Optionally, articles described herein further comprise a functionallayer (i.e., at least one of a transparent conductive layer or a gasbarrier layer) disposed between the first major surface of a substrateand a layer of material described herein. Optionally, articles describedherein further comprise a functional layer (i.e., at least one of atransparent conductive layer or a gas barrier layer) disposed on a layerof material described herein.

Optionally, articles described herein further comprise a (second) layerof material (including those described herein and those described in PCTAppl. Nos. US2011/026454, filed Feb. 28, 2011, and U.S. Pat. Appl. Nos.61/452,403 and 61/452,430, filed Mar. 14, 2011, the disclosures of whichare incorporated herein by reference) on the second major surface of asubstrate. Optionally, articles described herein further comprise afunctional layer (i.e., at least one of a transparent conductive layeror a gas barrier layer) disposed between the second major surface of asubstrate and a (second) layer of material. Optionally, articlesdescribed herein further comprise a functional layer (i.e., at least oneof a transparent conductive layer or a gas barrier layer) disposed on a(second) layer of material.

Articles described herein can be used, for example, for creating highperformance, low fringing, antireflective optical articles. When afunctional layer (i.e., at least one of a transparent conductive layeror a gas barrier layer) is disposed on a layer of material describedherein, articles described herein may have significantly enhancedoptical performance.

Embodiments of nanostructured materials and articles described hereinare useful for numerous applications including optical andoptoelectronic devices, displays, solar cells, light sensors, eye wear,camera lenses, and glazing.

DETAILED DESCRIPTION

Typically, the nanostructured material comprises a polymeric matrix anda nanoscale dispersed phase. In some embodiments, the polymeric matrixcomprises at least one of acrylate, urethane acrylate, methacrylate,polyester, epoxy, fluoropolymer, or siloxane.

The polymeric matrix can be made from reactive precursors. Examples ofprecursors include polymerizable resins comprising at least oneoligomeric urethane (meth)acrylate. Typically the oligomeric urethane(meth)acrylate is multi(meth)acrylate. The term “(meth)acrylate” is usedto designate esters of acrylic and methacrylic acids, and“multi(meth)acrylate” designates a molecule containing more than one(meth)acrylate group, as opposed to “poly(meth)acrylate” which commonlydesignates (meth)acrylate polymers. Typically, the multi(meth)acrylateis a di(meth)acrylate, although other examples includetri(meth)acrylates and tetra(meth)acrylates.

Oligomeric urethane multi(meth)acrylates are available, for example,from Sartomer under the trade designation “PHOTOMER 6000 Series” (e.g.,“PHOTOMER 6010” and “PHOTOMER 6020”), under the trade designation “CN900 Series” (e.g., “CN966B85”, “CN964”, and “CN972”). Oligomericurethane (meth)acrylates are also available, for example, from SurfaceSpecialties under the trade designations “EBECRYL 8402”, “EBECRYL 8807”,and “EBECRYL 4827”. Oligomeric urethane (meth)acrylates may also beprepared, for example, by the initial reaction of an alkylene oraromatic diisocyanate of the formula OCN—R3-NCO, wherein R3 is a C2-100alkylene or an arylene group with a polyol. Typically, the polyol is adiol of the formula HO—R4-OH, wherein R4 is a C2-100 alkylene group.Dependant on the stoichiometry of the reagents the intermediate productis then a urethane diol or diisocyanate, which subsequently can undergoreaction with an isocyanate functional vinyl monomer, such as2-isocyanatoethyl(meth)acrylate, respectively a 2-hydroxyalkyl(meth)acrylate. Suitable diisocyanates include 2,2,4-trimethylhexylenediisocyanate and toluene diisocyanate. Alkylene diisocyanates aregenerally preferred. In one case, compound of this type may be preparedfrom 2,2,4-trimethylhexylene diisocyanate, poly(caprolactone)diol, and2-hydroxyethyl methacrylate. In at least some cases, the urethane(meth)acrylate is preferably aliphatic.

The polymerizable precursors can be radiation curable compositionscomprising at least one other monomer (i.e., other than an oligomericurethane (meth)acrylate). The other monomer may reduce viscosity and/orimprove thermomechanical properties and/or increase refractive index.Monomers having these properties include acrylic monomers (i.e.,acrylate and methacrylate esters, acrylamides, and methacrylamides),styrene monomers, and ethylenically unsaturated nitrogen heterocycles.Examples of UV curable acrylate monomers from Sartomer include “SR238”,“SR351”, “SR399”, and “SR444”.

Suitable acrylic monomers include monomeric (meth)acrylate esters. Theyinclude alkyl (meth)acrylates (e.g., methyl acrylate, ethyl acrylate,1-propyl acrylate, methyl methacrylate, 2-ethylhexylacrylate,isobornyl(meth)acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate,isooctyl acrylate, ethoxyethoxyethyl acrylate, methoxyethoxyethylacrylate, and t-butyl acrylate). Also included are (meth)acrylate estershaving other functionality. Compounds of this type are illustrated byethoxyethoxyethyl acrylate, methoxyethoxyethyl acrylate,tetrahydrofurfuryl acrylate, 2-(N-butylcarbamyl)ethyl (meth)acrylate,2,4-dichlorophenyl acrylate, 2,4,6-tribromophenyl acrylate,tribromophenoxyethyl acrylate, t-butylphenyl acrylate, phenyl acrylate,phenyl thioacrylate, phenylthioethyl acrylate, alkoxylated phenylacrylate, isobornyl acrylate, and phenoxyethyl acrylate. The reactionproduct of tetrabromobisphenol A diepoxide, and (meth)acrylic acid isalso suitable.

The other monomer may also be a monomeric N-substituted orN,N-disubstituted (meth)acrylamide, especially an acrylamide. Theseinclude N-alkylacrylamides and N,N-dialkylacrylamides, especially thosecontaining C1-4 alkyl groups. Examples are N-isopropylacrylamide,N-t-butylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

The other monomer may further be a polyol multi(meth)acrylate. Suchcompounds are typically prepared from aliphatic diols, triols, and/ortetraols containing 2-10 carbon atoms. Examples of suitablepoly(meth)acrylates are ethylene glycol diacrylate, 1,6-hexanedioldiacrylate, 2-ethyl-2-hydroxymethyl-1,3-propanediol triacylate(trimethylolpropane triacrylate), di(trimethylolpropane) tetraacrylate,pentaerythritol tetraacrylate, the corresponding methacrylates, and the(meth)acrylates of alkoxylated (usually ethoxylated) derivatives of saidpolyols. Monomers having at least two (ethylenically unsaturated groupscan serve as a crosslinker.

Styrenic compounds suitable for use as the other monomer includestyrene, dichlorostyrene, 2,4,6-trichlorostyrene, 2,4,6-tribromostyrene,4-methylstyrene, and 4-phenoxystyrene. Ethylenically unsaturatednitrogen heterocycles include N-vinylpyrrolidone and vinylpyridine.

Additional examples of polymerizable precursors includetetrafluoroethylene, vinylfluoride, vinylidene fluoride,chlorotrifluoroethylene, perfluoroakoxy, fluorinated ethylene-propylene,ethylenetetrafluoroethylene, ethylenechlorotrifluoroethylene,perfluoropolyether, perfluoropolyoxetane, hexafluoropropylene oxide,siloxane, organosilicon, siloxides, ethylene oxide, propylene oxide,acrylamide, amine, ether, sulfonate, acrylic acid, maleic anhydride,vinyl acid, vinyl alcohol, vinylpyridine, or vinylpyrrolidone.

The nano-scale phase is a discontinuous phase randomly dispersed withinthe polymeric matrix, and can comprise nanoparticles (e.g., nanospheresand nanocubes), nanotubes, nanofibers, caged molecules, andhyperbranched molecules). The nano-scale dispersed phase can beassociated or unassociated or both. The nano-scale dispersed phase canbe well dispersed. Well dispersed means little agglomeration. Theaverage dimension of the nanoscale phase can be ranged from 1 nm to 100nm.

In some embodiments, nanostructured materials described herein thenanoscale phase is present in less than 1.25 wt. % (in some embodiments,less 1 wt. %, 0.75 wt. %, 0.5 wt. %, or even less than 0.35 wt. %),based on the total weight of the polymeric matrix and nanoscale phase.

In some embodiments, nanostructured materials described herein includethe nanoscale phase in a range from 60 nm to 90 nm in size, in a rangefrom 30 nm to 50 in size, and less than 25 nm in size, wherein thenanoscale phase is present in a range from 0.25 wt. % to 50 wt. % (insome embodiments, 1 wt. % to 25 wt. %, 5 wt. % to 25 wt. %, or even 10wt. % to 25 wt. %) for sizes in the range from 60 nm to 90 nm, 1 wt. %to 50 wt. % (in some embodiments, 1 wt. % to 25 wt. %, or even 1 wt. %to 10 wt. %) for sizes in the range from 30 nm to 50 nm, and 0.25 wt. %to 25 wt. % (in some embodiments, 0.5 wt. % to 10 wt. %, 0.5 wt. % to 5wt. %, or even 0.5 wt. % to 2 wt. %) for sizes less than 25 nm, based onthe total weight of the polymeric matrix and nanoscale phase.

In some embodiments, nanostructured materials described herein includedthe nanoscale phase in a range from 60 nm to 90 nm in size, in a rangefrom 30 nm to 50 in size, and less than 25 nm in size, wherein thenanoscale phase is present in a range from 0.1 vol. % to 35 vol. % (insome embodiments, 0.5 vol. % to 25 vol. %, 1 vol. % to 25 vol. %, oreven 3 vol. % to 15 vol. %) for sizes in a range from 60 nm to 90 nm,0.1 vol. % to 25 vol. % (in some embodiments, 0.25 vol. % to 10 vol. %,or even 0.25 vol. % to 5 vol. %) for sizes in a range from 30 nm to 50nm, and 0.1 vol. % to 10 vol. % (in some embodiments, 0.25 vol. % to 10vol. %, or even 0.1 vol. % to 2.5 vol. %) for sizes less than 25 nm,based on the total volume of the polymeric matrix and nanoscale phase.

In some embodiments, nanostructured materials described herein exhibit arandom anisotropic nanostructured surface. The nano-structuredanisotropic surface typically comprises nanofeatures having a height towidth ratio of at least 2:1 (in some embodiments, at least 5:1, 10:1,25:1, 50:1, 75:1, 100:1, 150:1, or even at least 200:1). Exemplarynanofeatures of the nano-structured anisotropic surface includenano-pillars or nano-columns, or continuous nano-walls comprisingnano-pillars, nano-columns, anistropic nano-holes, or anisotropicnano-pores. In some embodiments, the nanofeatures have steep side wallsthat are roughly perpendicular to the functional layer-coated substrate.In some embodiments, the nano features are capped with dispersed phasematerial. The average height of the nanostructured surface can be from200 nm to 500 nm with a standard deviation ranged from 20 nm to 75 nm.The nanostructural features are essentially randomized in the planardirection, and in some cases also in the z-direction.

In some embodiments of nanostructured materials described herein havingthe nanostructured material comprising the nanoscale phase, thenanoscale phase comprises submicrometer particles. In some embodiments,the submicrometer particles have an average particle size in a rangefrom 1 nm to 100 nm (in some embodiments, 1 nm to 75 nm, 1 nm to 50 nm,or even 1 nm to 25 nm). In some embodiments, the submicrometer particlesare covalently bonded to the polymeric matrix.

The sub-micrometer particles can comprise carbon, metals, metal oxides(e.g., SiO₂, ZrO₂, TiO₂, ZnO, magnesium silicate, indium tin oxide, andantimony tin oxide), carbides (e.g., SiC and WC), nitrides, borides,halides, fluorocarbon solids (e.g., poly(tetrafluoroethylene)),carbonates (e.g., calcium carbonate), and mixtures thereof. In someembodiments, sub-micrometer particles comprises at least one of SiO₂particles, ZrO₂ particles, TiO₂ particles, ZnO particles, Al₂O₃particles, calcium carbonate particles, magnesium silicate particles,indium tin oxide particles, antimony tin oxide particles,poly(tetrafluoroethylene) particles, or carbon particles. Metal oxideparticles can be fully condensed. Metal oxide particles can becrystalline.

In some embodiments, the sub-micrometer particles can be monodisperse(all one size or unimodal) or have a distribution (e.g., bimodal, orother multimodal).

Exemplary silicas are commercially available, for example, from NalcoChemical Co., Naperville, Ill., under the trade designation “NALCOCOLLOIDAL SILICA,” such as products 2329, 2329K, and 2329 PLUS.Exemplary fumed silicas include those commercially available, forexample, from Evonik Degusa Co., Parsippany, N.J., under the tradedesignation, “AEROSIL series OX-50”, as well as product numbers -130,-150, and -200; and from Cabot Corp., Tuscola, Ill., under thedesignations “CAB-O-SPERSE 2095”, “PG002”, “PG022”, “CAB-O-SPERSE A105”,and “CAB-O-SIL M5”. Other exemplary colloidal silica are available, forexample, from Nissan Chemicals under the designations “MP1040”,“MP2040”, “MP3040”, and “MP4040”.

In some embodiments, the sub-micrometer particles are surface modified.Preferably, the surface-treatment stabilizes the sub-micrometerparticles so that the particles are well dispersed in the polymerizableresin, and result in a substantially homogeneous composition. Thesub-micrometer particles can be modified over at least a portion of itssurface with a surface treatment agent so that the stabilized particlescan copolymerize or react with the polymerizable resin during curing.

In some embodiments, the sub-micrometer particles are treated with asurface treatment agent. In general, a surface treatment agent has afirst end that will attach to the particle surface (covalently,ionically or through strong physisorption) and a second end that impartscompatibility of the particle with the resin and/or reacts with theresin during curing. Examples of surface treatment agents includealcohols, amines, carboxylic acids, sulfonic acids, phosphonic acids,silanes, and titanates. The preferred type of treatment agent isdetermined, in part, by the chemical nature of the metal oxide surface.Silanes are preferred for silica and other siliceous fillers. Silanesand carboxylic acids are preferred for metal oxides, such as zirconia.The surface modification can be done either subsequent to mixing withthe monomers or after mixing. It is preferred in the case of silanes toreact the silanes with the particles or nanoparticle surface beforeincorporation into the resins. The required amount of surface modifieris dependent on several factors such as particle size, particle type,molecular weight of the modifier, and modifier type.

Representative embodiments of surface treatment agents include compoundssuch as isooctyl tri-methoxy-silane,N-(3-triethoxysilylpropyl)methoxyethoxy-ethoxyethyl carbamate (PEG3TES),N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate (PEG2TES),3-(methacryloyloxy)propyltrimethoxysilane,3-acryloxypropyltrimethoxysilane,3-(methacryloyloxy)propyltriethoxysilane,3-(methacryloyloxy)propylmethyldimethoxysilane,3-(acryloyloxypropyl)methyldimethoxysilane,3-(methacryloyloxy)propyldimethylethoxysilane,vinyldimethylethoxysilane, phenyltrimethoxysilane,n-octyltrimethoxysilane, dodecyltrimethoxysilane,octadecyltrimethoxysilane, propyltrimethoxysilane,hexyltrimethoxysilane, vinylmethyldiactoxysilane,vinylmethyldiethoxysilane, vinyltriacetoxysilane, vinyltriethoxysilane,vinyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane,vinyltri-t-butoxysilane, vinyltris-isobutoxysilane,vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane,styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid, oleicacid, stearic acid, dodecanoic acid, 2-(2-(2-methoxyethoxy)ethoxy)aceticacid (MEEAA), beta-carboxyethylacrylate, 2-(2-methoxyethoxy)acetic acid,methoxyphenyl acetic acid, and mixtures thereof. One exemplary silanesurface modifier is available, for example, from OSI Specialties,Crompton South Charleston, W. Va., under the trade designation “SILQUESTA1230”. For mono-functional silane coupling agents comprising silanolgroups, the silane agents can react and form covalent bonds with thehydroxyl groups on the surface of nanopartilces. For bi ormulti-functional silane coupling agents comprising silanol groups andother functional groups (e.g., acrylate, epoxy, and/or vinyl), thesilane agents can react and form covalent bonds with the hydroxyl groupson the surface of nanoparticles and the functional groups (e.g.,acrylate, epoxy, and/or vinyl) in the polymeric matrix.

Surface modification of the particles in the colloidal dispersion can beaccomplished in a variety of ways. The process involves the mixture ofan inorganic dispersion with surface modifying agents. Optionally, aco-solvent can be added at this point, such as 1-methoxy-2-propanol,ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, and1-methyl-2-pyrrolidinone. The co-solvent can enhance the solubility ofthe surface modifying agents as well as the surface modified particles.The mixture comprising the inorganic sol and surface modifying agents issubsequently reacted at room or an elevated temperature, with or withoutmixing. In one method, the mixture can be reacted at about 85° C. forabout 24 hours, resulting in the surface modified sol. In anothermethod, where metal oxides are surface modified, the surface treatmentof the metal oxide can preferably involve the adsorption of acidicmolecules to the particle surface. Surface modification of the heavymetal oxide preferably takes place at room temperature.

Surface modification of ZrO₂ with silanes can be accomplished underacidic conditions or basic conditions. In one example, the silanes areheated under acid conditions for a suitable period of time. At whichtime the dispersion is combined with aqueous ammonia (or other base).This method allows removal of the acid counter ion from the ZrO₂ surfaceas well as reaction with the silane. In another method, the particlesare precipitated from the dispersion and separated from the liquidphase.

A combination of surface modifying agents can be useful, for example,wherein at least one of the agents has a functional groupco-polymerizable with a crosslinkable resin. For example, thepolymerizing group can be ethylenically unsaturated or a cyclic groupsubject to ring opening polymerization. An ethylenically unsaturatedpolymerizing group can be, for example, an acrylate or methacrylate, orvinyl group. A cyclic functional group subject to ring openingpolymerization generally contains a heteroatom, such as oxygen, sulfur,or nitrogen, and preferably a 3-membered ring containing oxygen (e.g.,an epoxide).

Optionally, at least some of the submicrometer particles arefunctionalized with at least one multifunctional silane coupling agentcomprising silanol and at least one of acrylate, epoxy, or vinylfunctional groups.

The coupling agents and submicronmeter particles are typically mixed insolvents allowing silanol of coupling agents to react with hydroxylgroups on the surface of submicronmeter particles and form covalentbonds with particles at elevated temperatures. The coupling agents formcovalent bonds with the submicronmeter particles providing sterichinderance between subsmicronmeter particles reducing or preventingaggregation and precipitation in solvents. Other functional groups onthe coupling agents such as acrylate, methacrylate, epoxy, or vinyl canfurther enhance the dispersion of the functionalized submicronmeterparticles in coating monomers or oligomers and in solvents.

In some embodiments, nanostructured materials described herein are inthe form of a layer. In some embodiments, the layer has a thickness ofat least 500 nm (in some embodiments, at least 1 micrometer, 1.5micrometer, 2 micrometer, 2.5 micrometers, 3 micrometers, 4 micrometers,5 micrometers, 7.5 micrometers, or even at least 10 micrometers.

In some embodiments, articles described herein, the layer furthercomprises in the range from 0.01 wt. % to 0.5 wt. % particles in therange from 1 micrometer to 10 micrometer particle in size. In someembodiments, articles described herein, the micrometer-scale particlescan be made from wax, polytetrafluoroethylene (PTFE),polymethylmethacrylate (PMMA), polystyrene, polylactic acid (PLA), orsilica. These micrometer-scale particles can be functionalized with thecoupling agents as described above and dispersed in coating solutions bya blender or sonicator. The particles are typically added to coatingresin binders in an amount in the range of 0.01-0.5 weight %, based onthe total amount of the resin binders constituting the coatings. Theparticles can form “undulation” (wavy protrusions/recesses) over theentire surface of the nanostructured material to form a surface shapewhich provided the anti-Newton ring property when in contact with thesurface of another material. This anti-Newton method can also be appliedwith other antireflective technologies such as traditional subwavelengthscale surface gratings, multilayer antireflective coatings, ultra-low orlow refractive index coatings using nano hollow sphere, porous fumedsilica, or any other nanoporous coating methods to provide anti-Newtonantireflective functionalities. Further details can be found, forexample, in U.S. Pat. No. 6,592,950 (Toshima et al.), the disclosure ofwhich is incorporated herein by reference.

Exemplary substrates include polymeric substrates, glass substrates orwindows, and functional devices (e.g., organic light emitting diodes(OLEDs), displays, and photovoltaic devices). Typically, the substrateshave thicknesses in a range from about 12.7 micrometers (0.0005 inch) toabout 762 micrometers (0.03 inch), although other thicknesses may alsobe useful.

Exemplary polymeric materials for the substrates include polyethyleneterephthalate (PET), polystyrene, acrylonitrile butadiene styrene,polyvinyl chloride, polyvinylidene chloride, polycarbonate,polyacrylates, thermoplastic polyurethanes, polyvinyl acetate,polyamide, polyimide, polypropylene, polyester, polyethylene,poly(methyl methacrylate), polyethylene naphthalate, styreneacrylonitrile copolymer, silicone-polyoxamide polymers, fluoropolymers,cellulose triacetate polymer, cyclic olefin copolymers, andthermoplastic elastomers. Semicrystalline polymers (e.g., polyethyleneterephthalate (PET)) may be particularly desirable for the applicationsrequiring good mechanical strength and dimensional stability. For otheroptical film applications, low birefringent polymeric substrates, suchas triacetate cellulose, poly(methyl methacrylate), polycarbonate, andcyclic olefin copolymers, may be particularly desirable to minimize oravoid orientation induced polarization or dichroism interference withother optical components, such as polarizer, electromagneticinterference, or conductive touch functional layer in the opticaldisplay devices.

The polymeric substrates can be formed, for example, by melt extrusioncasting, melt extrusion calendaring, melt extrusion with biaxialstretching, blown film processes, and solvent casting optionally withbiaxial stretching. In some embodiments, the substrates are highlytransparent (e.g., at least 90% transmittance in the visible spectrum)with low haze (e.g., less than 1%) and low birefringence (e.g., lessthan 50 nanometers optical retardance). In some embodiments, thesubstrates have a microstructured surface or fillers to provide hazy ordiffusive appearance.

Optionally, the substrate is a polarizer (e.g., a reflective polarizeror an absorptive polarizer). A variety of polarizer films may be used asthe substrate, including multilayer optical films composed, for example,of some combination of all birefringent optical layers, somebirefringent optical layers, or all isotropic optical layers. Themultilayer optical films can have ten or less layers, hundreds, or eventhousands of layers. Exemplary multilayer polarizer films include thoseused in a wide variety of applications such as liquid crystal displaydevices to enhance brightness and/or reduce glare at the display panel.The polarizer film may also be the type used in sunglasses to reducelight intensity and glare. The polarizer film may comprise a polarizerfilm, a reflective polarizer film, an absorptive polarizer film, adiffuser film, a brightness enhancing film, a turning film, a mirrorfilm, or a combination thereof. Exemplary reflective polarizer filmsinclude those reported in U.S. Pat. No. 5,825,543 (Ouderkirk et al.)U.S. Pat. No. 5,867,316 (Carlson et al.), U.S. Pat. No. 5,882,774 (Jonzaet al.), U.S. Pat. No. 6,352,761 B1 (Hebrink et al.), U.S. Pat. No.6,368,699 B1 (Gilbert et al.), and U.S. Pat. No. 6,927,900 B2 (Liu etal.), U.S. Pat. Appl. Pub. Nos. 2006/0084780 A1 (Hebrink et al.), and2001/0013668 A1 (Neavin et al.), and PCT Pub. Nos. WO95/17303 (Ouderkirket al.), WO95/17691 (Ouderkirk et al), WO95/17692 (Ouderkirk et al.),WO95/17699 (Ouderkirk et al.), WO96/19347 (Jonza et al.), WO97/01440(Gilbert et al.), WO99/36248 (Neavin et al.), and WO99/36262 (Hebrink etal.), the disclosures of which are incorporated herein by reference.Exemplary reflective polarizer films also include those commerciallyavailable from 3M Company, St. Paul, Minn., under the trade designations“VIKUITI DUAL BRIGHTNESS ENHANCED FILM (DBEF)”, “VIKUITI BRIGHTNESSENHANCED FILM (BEF)”, “VIKUITI DIFFUSE REFLECTIVE POLARIZER FILM(DRPF)”, “VIKUITI ENHANCED SPECULAR REFLECTOR (ESR)”, and “ADVANCEDPOLARIZER FILM (APF)”. Exemplary absorptive polarizer films arecommercially available, for example, from Sanritz Corp., Tokyo, Japan,under the trade designation of “LLC2-5518SF”.

The optical film may have at least one non-optical layer (i.e., alayer(s) that does not significantly participate in the determination ofthe optical properties of the optical film). The non-optical layers maybe used, for example, to impart or improve mechanical, chemical, oroptical, properties; tear or puncture resistance; weatherability; orsolvent resistance.

Exemplary glass substrates include sheet glass (e.g., soda-lime glass)such as that made, for example, by floating molten glass on a bed ofmolten metal. Other exemplary glass substrates include borosilicateglass, LCD glass and chemically strengthened glass. In some embodiments(e.g., for architectural and automotive applications), it may bedesirable to include a low-emissivity (low-E) coating on a surface ofthe glass to improve the energy efficiency of the glass. Other coatingsmay also be desirable in some embodiments to enhance theelectro-optical, catalytic, or conducting properties of glass.

One method for making nanostructured materials described hereincomprises:

-   -   providing a polymeric matrix comprising a nanodispersed phase;        and    -   anisotropically etching the polymeric matrix using plasma to        form a random nanostructured surface.        In some embodiments, the matrix is etched to a depth of at least        in a range from 200 nm to 500 nm. Highly directional ionized        plasma etching under high vacuum with high biased voltage, for        example, can enable deeper etching for greater than 200 nm.        Effective directional reactive and physical ions bombardments        are formed under high vacuum and biased voltage to allow deeper        penetration of plasma into the surface while minimizing side        etching.

Another method for making nanostructured materials described hereincomprises:

providing a polymeric matrix comprising a nanodispersed phase; and

etching at least a portion of the polymeric matrix using plasma (e.g.,O₂, Ar, CO₂, O₂/Ar, O₂/CO₂, C₆F₁₄/O₂, or C₃F₈/O₂ plasma) to form arandom nanostructured surface. Optionally. the nanostructured surface istreated at least a second time with plasma. In some embodiments, themethod is performed roll-to-roll using cylindrical reactive ion etching.In some embodiments, the etching is carried out at a pressure of about 1mTorr to about 20 mTorr.

Nanostructured materials described herein exhibit an average reflectionat 60 degrees off angle less than 1 percent (in some embodiments, lessthan 0.75, 0.5, 0.25, or less than 0.2 percent). The reflection at 60degree off angle is measured by Procedure 2 in the Examples below.

In another aspect, nanostructured materials described herein have areflection less than 2 percent (in some embodiments, less than 1.5percent or even less than 0.5 percent) as measured by Procedure 2 in theExamples below. The nanostructured materials described herein can have ahaze less than 3 percent (in some embodiments, less than 2 percent, 1.5percent, or even less than 1 percent) as measured by Procedure 3 in theExamples below.

For articles comprising, in order, a substrate, functional layer, and alayer of nanostructured material described herein, the article can bemade, for example, by a method comprising:

providing a substrate having first and second generally opposed majorsurfaces and the functional layer having opposing first and second majorsurfaces, wherein the first major surface of the functional layer isdisposed on the first major surface of the substrate;

coating a composition comprising at least one of a polymeric matrix or apolymeric precursor matrix and a nano-scale dispersed phase in the atleast one of the polymeric matrix or the polymeric precursor matrix onthe first major surface of the functional layer;

optionally drying the coating (and optionally curing the dried coating)to provide an article comprising the at least one of the polymericmatrix or the polymeric precursor matrix and a nano-scale dispersedphase in the at least one of the polymeric matrix or the polymericprecursor matrix;

exposing the second major surface of the article to reactive ionetching, wherein the ion etching comprises:

placing the article on a cylindrical electrode in a vacuum vessel;

introducing etchant gas to the vacuum vessel at a predetermined pressure(e.g., in a range from 1 milliTorr to 20 milliTorr);

generating plasma (e.g., an oxygen plasma) between the cylindricalelectrode and a counter-electrode;

rotating the cylindrical electrode to translate the substrate; and

anisotropically etching the coating to provide the randomnano-structured anisotropic surface.

For composites further comprising in order relative to the substrate, asecond functional layer, and a second nano-structured article, themethod can be conducted, for example, by providing the substrate withthe functional layer (which may be the same of different) on each majorsurface of the substrate, and applying the second nano-structuredarticle on the functional layer as described above in the method. Insome embodiments, the second nano-structured article is appliedsimultaneously with the first nano-structured article. In someembodiments, the second functional layer is provided after the firstnano-structured article applied, while in others, for example, duringthe application of the first nano-structured article.

For composites described herein comprising, in order, a substrate, alayer of nanostructured material described herein, and a functionallayer, the composite can be made, for example, by a method comprising:

providing a substrate having first and second generally opposed majorsurfaces;

coating a composition comprising at least one of a polymeric matrixmaterial or a polymeric precursor matrix and a nano-scale dispersedphase in the at least one of the polymeric matrix or the polymericprecursor matrix on the first major surface of the substrate;

optionally drying the coating (and optionally curing the dried coating)to provide an article comprising the at least one of the polymericmatrix or the polymeric precursor matrix and a nano-scale dispersedphase in the at least one of polymeric matrix or the polymeric precursormatrix;

exposing a major surface of the article to reactive ion etching, whereinthe ion etching comprises:

placing the article on a cylindrical electrode in a vacuum vessel;

introducing etchant gas to the vacuum vessel at a predetermined pressure(e.g., in a range from 1 milliTorr to 20 milliTorr);

generating plasma (e.g., an oxygen plasma) between the cylindricalelectrode and a counter-electrode;

rotating the cylindrical electrode to translate the substrate; and

anisotropically etching the coating to provide the first randomnano-structured anisotropic surface; and

disposing a functional layer on the random nano-structured anisotropicsurface.

For composites further comprising in order relative to the substrate, asecond nano-structured article, and a second functional layer, saidmethod can be conducted, for example, by applying the secondnano-structured article on the functional layer as described above inthe method, and then disposing a functional layer (which may be the sameor different) on a major surface of the second nano-structured article.In some embodiments, the second nano-structured article is appliedsimultaneously with the first nano-structured article. In someembodiments, the second functional layer is provided after the firstnano-structured article applied, while in others, for example, duringthe application of the first nano-structured article.

There are several deposition techniques used to form the transparentconductive films, including chemical vapor deposition (CVD), magnetronsputtering, evaporation, and spray pyrolysis. Glass substrates have beenwidely used for making organic light emitting diodes. Glass substrates,however, tend to be undesirable for certain applications (e.g.,electronic maps and portable computers). Where flexibility is desired,glass is brittle and hence undesirable. Also, for some applications(e.g., large area displays) glass is too heavy. Plastic substrates arean alternative to glass substrates. The growth of transparent conductivefilms on plastic substrates by low temperature (25° C.-125° C.)sputtering is reported, for example, by Gilbert et al., 47^(th) AnnualSociety of Vacuum Coaters Technical Conference Proceedings (1993), T.Minami et al., Thin Solid Film, Vol. 270, page 37 (1995), and J. Ma,Thin Solid Films, vol. 307, page 200 (1997). Another depositiontechnique, pulsed laser deposition, is reported, for example, in U.S.Pat. No. 6,645,843 (Kim et al.), wherein a smooth, low electricalresistivity indium-tin-oxide (ITO) coating is formed on a polyethyleneterephthalate (PET) substrate. The electrically-conductive layer caninclude a conductive elemental metal, a conductive metal alloy, aconductive metal oxide, a conductive metal nitride, a conductive metalcarbide, a conductive metal boride, and combinations thereof. Preferredconductive metals include elemental silver, copper, aluminum, gold,palladium, platinum, nickel, rhodium, ruthenium, aluminum, and zinc.Alloys of these metals, such as silver-gold, silver-palladium,silver-gold-palladium, or dispersions containing these metals inadmixture with one another or with other metals also can be used.Transparent conductive oxides (TCO), such as indium-tin-oxide (ITO),indium-zinc-oxide (IZO), zinc oxide, with or without, dopants, such asaluminum, gallium and boron, other TCOs, and combinations thereof canalso be used as an electrically-conductive layer. Preferably, thephysical thickness of an electrically-conductive metallic layer is in arange from about 3 nm to about 50 nm (in some embodiments, about 5 nm toabout 20 nm), whereas the physical thickness of the transparentconductive oxide layers are preferably in a range from about 10 nm toabout 500 nm (in some embodiments, about 20 nm to about 300 nm). Theresulting electrically-conductive layer can typically provide a sheetresistance of less than 300 ohms/sq. (in some embodiments, less than 200ohms/sq., or even less than 100 ohms/sq.). For functional layers appliedto a structured surface, the layer may follow the surface contour of thestructured surface so that the antireflection function is created at theinterface between the structured surface and the deposited layer, and atthe second surface of the functional coating layer contacting air or thesurface of another substrate.

Transparent conductive films can be made, for example, from transparentconductive polymers. Conductive polymers include derivatives ofpolyacetylene, polyaniline, polypyrrole, PETOT/PSS(poly(3,4-ethylenedioxythiophene)/polystyrenesulfonic acid), orpolythiophenes (see, e.g., Skotheim et al., Handbook of ConductingPolymers, 1998). Although not wanting to be bound by theory, it isbelieved that these polymers have conjugated double bonds which allowfor conduction. Further, although not wanting to be bound by theory, itis believed that by manipulating the band structure, polythiophenes havebeen modified to achieve a HUMO-LUMO separation that is transparent tovisible light. In a polymer, the band structure is determined by themolecular orbitals. The effective bandgap is the separation between thehighest occupied molecular orbital (HOMO) and lowest unoccupiedmolecular orbital (LUMO).

The transparent conductive layer can comprise, for example, anisotropicnano-scale materials which can be solid or hollow. Solid anisotropicnano-scale materials include nanofibers and nanoplatelets. Hollowanisotropic nano-scale materials include nanotubes. Typically, thenanotube has an aspect ratio (length:diameter) greater than 10:1 (insome embodiments, greater than 50:1, or even greater than 100:1). Thenanotubes are typically greater than 500 nm (in some embodiments,greater than 1 micrometer, or even greater than 10 micrometers) inlength. These anisotropic nano-scale materials can be made from anyconductive material. Most typically, the conductive material ismetallic. The metallic material can be an elemental metal (e.g.,transition metals) or a metal compound (e.g., metal oxide). The metallicmaterial can also be a metal alloy or a bimetallic material, whichcomprises two or more types of metal. Suitable metals include silver,gold, copper, nickel, gold-plated silver, platinum, and palladium. Theconductive material can also be non-metallic (e.g., carbon or graphite(an allotrope of carbon)).

Gas (e.g., water vapor and oxygen) barrier films typically comprise arelatively thin (e.g., about 100 nm to about 300 nm) layer of a metaloxide, such as aluminum oxide, magnesium oxide, or silicon oxide on afilm surface. Other exemplary layers on films to provide a gas barrierfilm include ceramics, such as silicon oxide, silicon nitride, aluminumoxide nitride, magnesium oxide, zinc oxide, indium oxide, tin oxide,tin-doped indium oxide, and aluminum-doped zinc oxide. Gas barrier filmscan be a single barrier layer or multiple barrier layers construction.The barrier layer may also comprise multifunctional properties such asconductive functionality.

In some embodiments, the surface of the polymeric matrix comprising thesub-micrometer particles may be microstructured. For example, atransparent conductive oxide-coated substrate, with a v-groovemicrostructured surface can be coated with polymerizable matrixmaterials comprising the sub-micrometer particles and treated by plasmaetching to form nanostructures on v-groove microstructured surface.Other examples include a fine micro-structured surface resulting fromcontrolling the solvent evaporation process from multi-solvent coatingsolutions, reported as in U.S. Pat. No. 7,378,136 (Pokorny et al.); orthe structured surface from the micro-replication method reported inU.S. Pat. No. 7,604,381 (Hebrink et al.); or any other structuredsurface induced, for example, by electrical and magnetic fields.

Optionally, articles described herein further comprise an opticallyclear adhesive disposed on the second surface of the substrate. Theoptically clear adhesives that may be used in the present disclosurepreferably are those that exhibit an optical transmission of at leastabout 90%, or even higher, and a haze value of below about 5% or evenlower, as measured on a 25 micrometer thick sample in the matterdescribed below in the Example section under the Haze and TransmissionTests for optically clear adhesive. Suitable optically clear adhesivesmay have antistatic properties, may be compatible with corrosionsensitive layers, and may be able to be released from the substrate bystretching the adhesive. Illustrative optically clear adhesives includethose described in PCT Pub. No. WO 2008/128073 (Everaerts et al.)relating to antistatic optically clear pressure sensitive adhesive; U.S.Pat. Appl. Pub. No. US 2009/0229732A1 (Determan et al.) relating tostretch releasing optically clear adhesive; U.S. Pat. Appl. Pub. No. US2009/0087629 (Everaerts et al.) relating to indium tin oxide compatibleoptically clear adhesive; U.S. Pat. Appl. Pub. No. US 2010/0028564(Everaerts et al.) relating to antistatic optical constructions havingoptically transmissive adhesive; U.S. Pat. Appl. Pub. No. 2010/0040842(Everaerts et al.) relating to adhesives compatible with corrosionsensitive layers; PCT Pub. No. WO 2009/114683 (Determan et al.) relatingto optically clear stretch release adhesive tape; and PCT Pub. No. WO2010/078346 (Yamanaka et al.) relating to stretch release adhesive tape.In one embodiment, the optically clear adhesive has a thickness of up toabout 5 micrometer.

In some embodiments, articles described herein further comprise ahardcoat comprising at least one of SiO₂ nanoparticles or ZrO₂nanoparticles dispersed in a crosslinkable matrix comprising at leastone of multi(meth)acrylate, polyester, epoxy, fluoropolymer, urethane,or siloxane (which includes blends or copolymers thereof). Commerciallyavailable liquid-resin based materials (typically referred to as“hardcoats”) may be used as the polymeric matrix or as a component ofthe polymeric matrix. Such materials include that available fromCalifornia Hardcoating Co., San Diego, Calif., under the tradedesignation “PERMANEW”; and from Momentive Performance Materials,Albany, N.Y., under the trade designation “UVHC”. Additionally,commercially available nanoparticle filled polymeric matrix materialsmay be used such as those available from Nanoresins AG, GeesthachtGermany, under the trade designations “NANOCRYL” and “NANOPDX”.

In some embodiments, the articles described herein further comprises asurface protection adhesive sheet (laminate premasking film) having areleasable adhesive layer formed on the entire area of one side surfaceof a film, such as a polyethylene film, a polypropylene film, a vinylchloride film, or a polyethylene terephthalate film to the surface ofthe articles, or by superimposing the above-mentioned polyethylene film,a polypropylene film, a vinyl chloride film, or a polyethyleneterephthalate film on the surface of articles.

Exemplary Embodiments

1A. A nanostructured material exhibiting a random anisotropicnanostructured surface, and exhibiting an average reflection at 60degrees off angle less than 1 percent (in some embodiments, less than0.75, 0.5, 0.25, or less than 0.2 percent).

2A. The nanostructured material of Embodiment 1A comprising a polymericmatrix and a nanoscale dispersed phase.

3A. The nanostructured material of Embodiment 2A, wherein the nanoscalephase is present in a range from 60 nm to 90 nm in size, in a range from30 nm to 50 in size, and less than 25 nm in size, and wherein thenanoscale phase is present in a range from 0.25 wt. % to 50 wt. % (insome embodiments, 1 wt. % to 25 wt. %, 5 wt. % to 25 wt. %, or even 10wt. % to 25 wt. %) for sizes in the range from 60 nm to 90 nm, 1 wt. %to 50 wt. % (in some embodiments, 1 wt. % to 25 wt. %, or even 1 wt. %to 10 wt. %) for sizes in a range from for sizes in the range from 30 nmto 50 nm, and 0.25 wt. % to 25 wt. % (in some embodiments, 0.5 wt. % to10 wt. %, 0.5 wt. % to 5 wt. %, or even 0.5 wt. % to 2 wt. %) for sizesless than 25 nm, based on the total weight of the polymeric matrix andnanoscale phase.4A. The nanostructured material of either Embodiment 2A or 3A, whereinthe nanoscale phase is present in a range from 60 nm to 90 nm in size,in a range from 30 nm to 50 in size, and less than 25 nm in size, andwherein the nanoscale phase is present in the range from 0.1 vol. % to35 vol. % (in some embodiments, 0.5 vol. % to 25 vol/%, 1 vol. % to 25vol. %, or even 3 vol. % to 15 vol. %) for sizes in the range from 60 nmto 90 nm, 0.1 vol. % to 25 vol. % (in some embodiments, 0.25 vol. % to10 vol. %, or even 0.25 vol. % to 5 vol. %) for sizes in a range from 30nm to 50 nm, and 0.1 vol. % to 10 vol. % (in some embodiments, 0.25 vol.% to 10 vol. %, or even 0.1 vol. % to 2.5 vol. %) for sizes less than 25nm, based on the total volume of the polymeric matrix and nanoscalephase.5A. The nanostructured material of any of Embodiments 2A to 4A, whereinat least a portion of the polymeric matrix comprises at least one oftetrafluoroethylene, vinylfluoride, vinylidene fluoride,chlorotrifluoroethylene, perfluoroakoxy, fluorinated ethylene-propylene,ethylenetetrafluoroethylene, ethylenechlorotrifluoroethylene,perfluoropolyether, perfluoropolyoxetane, hexafluoropropylene oxide,siloxane, organosilicon, siloxides, silyl halides, ethylene oxide,propylene oxide, acrylamide, amine, ether, sulfonate, acrylic acid,maleic anhydride, vinyl acid, vinyl alcohol, vinylpyridine, orvinylpyrrolidone.6A. The nanostructured material of any preceding Embodiment A, whereinthe nanoscale phase comprises submicrometer particles.7A. The nanostructured material of Embodiment 6A, wherein thesubmicrometer particles have an average particle size in a range from 1nm to 100 nm (in some embodiments, 1 nm to 75 nm, 1 nm to 50 nm, or even1 nm to 25 nm), and wherein the nanoscale phase is present in less than1.25 wt. % (in some embodiments, less 1 wt. %, 0.75 wt. %, 0.5 wt. %, oreven less than 0.35 wt. %), based on the total weight of the polymericmatrix and nanoscale phase.8A. The nanostructured material of either Embodiment 2A to 7A, whereinthe submicrometer particles are covalently bonded to the polymericmatrix.9A. The nanostructured material of any of Embodiments 2A to 8A, whereinat least some of the submicrometer particles are functionalized with atleast one multifunctional silane coupling agent comprising silanol andat least one of acrylate, epoxy, or vinyl functional groups.10A. The nanostructured material of any of Embodiments 2A to 9A, whereinthe submicrometer particles comprise at least one of carbon, metal,metal oxide, metal carbide, metal nitride, or diamond.11A. The nanostructured material of any of Embodiments 2A to 10A, thepolymeric matrix (e.g., cross linkable material) comprises at least oneof acrylate, urethane acrylate, methacrylate, polyester, epoxy,fluoropolymer, or siloxane.12A. The nanostructured material of any preceding Embodiment A, whereinthe nanostructured anisotropic surface comprises nanoscale featureshaving a height to width ratio of at least 2:1 (in some embodiments, atleast 10:1).13A. The nanostructured material of any preceding Embodiment A that is alayer.14A. The layer of Embodiment 13A having a thickness of at least 500 nm(in some embodiments, at least 1 micrometer, 1.5 micrometer, 2micrometer, 2.5 micrometers, 3 micrometers, 4 micrometers, 5micrometers, 7.5 micrometers, or even at least 10 micrometers).15A. An article comprising a substrate having first and second generallyopposed major surfaces with the layer of either Embodiment 13A or 14A onthe first major surface.16A. The article of Embodiment 15A, wherein the substrate is a polarizer(e.g., reflective polarizer or absorptive polarizer).17A. The article of either Embodiment 15A or 16A, wherein the firstmajor surface of the substrate has a microstructured surface.18A. The article of any of Embodiments 15A to 17A having a haze lessthan 2 percent (in some embodiments, less than 1.5 percent, 1 percent,0.75 percent, 0.5 percent or even less than 0.3 percent).19A. The article of any of Embodiments 15A to 18A further comprising ahardcoat comprising at least one of SiO₂ nanoparticles or ZrO₂nanoparticles dispersed in a crosslinkable matrix comprising at leastone of multi(meth)acrylate, polyester, epoxy, fluoropolymer, urethane,or siloxane.20A. The article of any of Embodiments 15A to 19A having a visible lighttransmission of at least 90 percent (in some embodiments, at least 94percent, 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, oreven 100 percent).21A. The article of any of Embodiments 15A to 20A, further comprising afunctional layer disposed between the first major surface of thesubstrate and the layer, wherein the functional layer is at least one ofa transparent conductive layer or a gas barrier layer.22A. The article of any of Embodiments 15A to 21A, further comprising apre-mask film disposed on the layer.23A. The article of any of Embodiments 15A to 21A, further comprising afunctional layer disposed on the layer, wherein this functional layer isat least one of a transparent conductive layer or a gas barrier layer.24A. The article of any of Embodiments 15A to 21A or 23A furthercomprising a functional layer disposed on the second major surface ofthe substrate, wherein this functional layer is at least one of atransparent conductive layer or a gas barrier layer.25A. The article of any of Embodiments 15A to 21A or 23A, furthercomprising an optically clear adhesive disposed on the second surface ofthe substrate, the optically clear adhesive having at least 90%transmission in visible light and less than 5% haze.26A. The article of Embodiment 25A further comprising a major surface ofa glass substrate attached to the optically clear adhesive.27A. The article of Embodiment 25A, further comprising a major surfaceof a polarizer substrate attached to the optically clear adhesive.28A. The article of Embodiment 25A further comprising a major surface ofa touch sensor attached to the optically clear adhesive.29A. The article of Embodiment 25A, further comprising a release linerdisposed on the second major surface of the optically clear adhesive.1B. A method of making the nanostructured material of any of Embodiments1A to 12A, the method comprising:

providing a polymeric matrix comprising a nanodispersed phase; and

anisotropically etching the polymeric matrix using plasma to form therandom nanostructured surface.

2B. The method of Embodiment 1B, wherein the polymeric matrix is etchedto a depth of at least in a range from 200 nm to 500 nm.

1C. A method of making the nanostructured material of any of Embodiments1A to 12A, the method comprising:

providing a polymeric matrix comprising a nanodispersed phase; and

etching at least a portion of the polymeric matrix using plasma to formthe random nanostructured surface.

2C. The method of Embodiment 1C further comprising treating thenanostructured surface with plasma a second time.

3C. The method of either Embodiment 1C or 2C, wherein the method isperformed roll-to-roll using cylindrical reactive ion etching.

4C. The method of any preceding Embodiment C, wherein the etching iscarried out at a pressure of about 1 mTorr to about 20 mTorr.

5C. The method of any preceding Embodiment C, wherein the plasma is O₂,Ar, CO₂, O₂/Ar, O₂/CO₂, C₆F₁₄/O₂, or C₃F₈/O₂ plasma.

Advantages and embodiments of this invention are further illustrated bythe following examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention. All parts andpercentages are by weight unless otherwise indicated.

EXAMPLES

Procedure 1—Plasma Treatment of Roll-to-Roll Samples

The cylindrical RIE apparatus shown in FIG. 1 of PCT Pub. No.WO2010/078306A2 (Moses et al.), published in 2010, the disclosure ofwhich is incorporated by reference, was used to treat polymeric film.The width of the drum electrode was 42.5 inches (108 cm). Pumping wascarried out by means of a turbo-molecular pump.

Rolls of polymeric film were mounted within the chamber, the filmwrapped around the drum electrode and secured to the take up roll on theopposite side of the drum. The unwind and take-up tensions weremaintained at 3 pounds (13.3 N). The chamber door was closed and thechamber pumped down to a base pressure of 5×10⁻⁴ Torr. Oxygen was thenintroduced into the chamber. The operating pressure was nominally 5mTorr. Plasma was generated by applying a power of 5000 watts of radiofrequency energy to the drum. The drum was rotated so that the film wastransported at a desired speed for the specific etching time as statedin the specific example. For a piece-part film, the sample was eitherattached to a web carrier or to the surface of drum electrode to betreated at a desired speed for the specific etching time as stated inthe specific example.

Procedure 2—Measurement of 60° Off Angle Average % Reflection

The average % reflection (% R) of the plasma treated surface wasmeasured using a UV/Vis/NIR Scanning Spectrophotometer (obtained fromPerkinElmer. Walthan, Mass., under the trade designation “PERKINELMERLAMBDA 950 URA UV-VIS-NIR SCANNING SPECTROPHOTOMETER”). One sample ofeach film was prepared by applying black vinyl tape to the backside ofthe sample. The black tape was laminated to the backside of the sampleusing a roller to ensure there were no air bubbles trapped between theblack tape and the sample. The front surface % reflection (specular) ofa sample was measured by placing the sample in the machine so that thenon-tape side was against the aperture. The % reflection was measured ata 60° off angle and average % reflection was calculated for thewavelength range of 400-700 nm.

Procedure 3—Measurement of Transmission and Haze

The measurement of average % transmission and haze was carried with ahaze meter (obtained under the trade designation “BYK HAZEGARD PLUS”from BYK Gardiner) according to ASTM D1003-11 (2011), the disclosures ofwhich are incorporated herein by reference.

Functionalized 15 nm SiO₂ Dispersion

A dispersion of functionalized 15 nm SiO₂ dispersed in UV curable resincomprising photoinitiator was obtained from Momentive PerformanceMaterials, Wilton, Conn., under the trade designation “UVHC8558”). Theweight percentage of 15 nm SiO₂ in the dispersion is about 20 wt. %.

Functionalized 75 nm SiO₂ Dispersion

400 gm of 75 nm silica particles (obtained from Nalco Chemical Co.,Naperville, Ill., under the trade designation “NALCO 2329K”) was chargedinto a 1 quart (0.95 liter) jar. Four hundred fifty grams of1-methoxy-2-propanol, 9.2 grams of 3-(Methacryloyloxy)propyltrimethoxysilane, and 0.23 gram of hindered amine nitroxide inhibitor (obtainedfrom Ciba Specialty Chemical, Inc., Tarrytown, N.Y., under the tradedesignation “PROSTAB 5128”) in water at 5 wt. % inhibitor were mixedtogether and added to the jar while stirring. The jar was sealed andheated to 80° C. for 16 hours to form a surface-modified silicadispersion. The water was further removed from the mixture via rotaryevaporation to form a solution of 42.4 percent by weight 75 nmSiO_(2 in) 1-methoxy-2-propanol.

Coating Monomers and Photo-Initiator

Trimethylolpropantriacrylate (TMPTA) and 1,6-hexanediol diacrylate(HDDA) were obtained from Sartomer, under the trade designation “SR351”and “SR238”, respectively. Photoinitiator was obtained from BASFSpecialty Chemicals under the trade designation “IRGACURE 184”).

Examples 1-9 and Comparative Examples 1-3

Coating compositions 1-6 for Examples 1-9 and Comparative Examples 1-3were prepared from mixing functionalized 15 nm SiO₂ dispersion(“UVHC8558”) with trimethylolpropantriacrylate (TMPTA) (obtained fromSartomer, Exton, Pa., under the trade designation “SR351”) and1,6-hexanediol diacrylate (HDDA) (obtained from Sartomer under the tradedesignation “SR238”) to form 40 wt. % solids in 1-methoxoy-2-propanol(PM) and methyl ethyl ketone (MEK). The compositions of coatingcompositions 1-6 are provided in Table 1, below.

TABLE 1 Wt. % 15 nm SiO₂ in coating 15 nm SiO₂ coating compositions(grams) (solid) “UVHC8558” “SR351” “SR238” PM MEK Composition 1 0.5 0.205.88 1.96 8.40 3.6 Composition 2 1 0.40 5.76 1.92 8.40 3.6 Composition 32 0.80 5.52 1.84 8.40 3.6 Composition 4 3 1.20 5.28 1.76 8.40 3.6Composition 5 4 1.60 5.04 1.68 8.40 3.6 Composition 6 6 2.40 4.56 1.528.40 3.6

These coatings compositions were applied on 80 micrometer thicktriacetate cellulose film (obtained from Fuji Film Corporation, Tokyo,Japan, under the trade designation “FUJI TAC FILM”) using a Meyer rod(#4 bar) coating device. The coated substrates were dried at roomtemperature inside a ventilated hood for 5 minutes, and then cured usinga UV processor equipped with a H-Bulb under a nitrogen atmosphere at 50fpm (15.24 meter/minute).

The cured coated films were then subjected to the 02 plasma etchingprocess described in Procedure 1 for various etching times (see Table 2,below). The optical properties of the etched samples were measuredaccording to Procedures 2 and 3, and are reported in Table 2, below.

TABLE 2 Wt. % Etching 60 Coating 15 nm time degree Trans- CompositionSiO₂ (sec) ave % R mission Haze Example 1 1 0.5 300 0.21 96.8 0.88Example 2 2 1 300 0.32 96.9 0.67 Example 3 3 2 300 0.90 96.8 0.77Example 4 4 3 300 0.50 96.6 1.22 Example 5 5 4 300 0.71 96.7 1.14Example 6 1 0.5 180 0.34 96.8 0.32 Example 7 2 1 180 0.83 96.8 0.37Example 8 1 0.5 150 0.46 96.7 0.25 Example 9 2 1 150 0.82 96.7 0.31 C 66 300 1.23 96.7 0.92 Example 1 C 6 6 180 1.71 96.7 0.41 Example 2 C 6 6150 2.08 96.6 0.33 Example 3

Examples 10-11

The coating composition for Examples 10-11 as prepared from mixingfunctionalized 75 nm SiO₂ dispersion with trimethylolpropantriacrylate(TMPTA) (“SR351”) and 1,6-hexanediol diacrylate (HDDA) (“SR238”) to form40 wt. % solids in 1-methoxoy-2-propanol (PM) and methyl ethyl ketone(MEK). The compositions are provided in Table 3, below.

TABLE 3 Wt. % 75 nm 75 nm SiO₂ coating compositions (grams) SiO₂ in 42.4wt % coating 75 nm SiO₂ (solid) dispersion “SR351 “SR238” PM MEK“IRG184” Composition 7 15 2.830 5.1 1.7 6.80 3.6 0.24

The coating composition was applied on 80 micrometers triacetatecellulose film (“FUJI TAC FILM”) using a Meyer rod (#4 bar) coatingdevice. The coated substrate was dried at room temperature inside aventilated hood for 5 minutes, and then cured using a UV processorequipped with a H-Bulb under a nitrogen atmosphere at 50 fpm (15.24meter/minute).

The cured coated films were then subjected to the O₂ plasma etchingprocess described in Procedure 1 for various etching times (see Table 4,below). The optical properties of the etched samples were measuredaccording to Procedures 2 and 3, and are reported in Table 4, below.

TABLE 4 Wt. % Etching 60 Coating 75 nm time degree Trans- CompositionSiO₂ (sec) ave % R mission Haze Example 7 15 150 0.95 97.2 0.43 10Example 7 15 180 0.88 97 0.65 11

Foreseeable modifications and alterations of this disclosure will beapparent to those skilled in the art without departing from the scopeand spirit of this invention. This invention should not be restricted tothe embodiments that are set forth in this application for illustrativepurposes.

What is claimed is:
 1. A method of making a nanostructured layercomprising a polymeric matrix and a nanoscale dispersed phase, the layerhaving a random anisotropic nanostructured surface, the randomanisotropic nanostructured surface having an average reflection at 60degrees off angle less than 1 percent, the layer having a thickness ofat least 500 nm, and the layer having a visible light transmissionthrough the thickness of the layer at 90 degrees to the randomanisotropic nanostructured surface of at least 94 percent, the methodcomprising: providing the polymeric matrix comprising the nanodispersedphase; and anisotropically etching the polymeric matrix using plasma toform the random nanostructured surface.
 2. A method of making ananostructured layer comprising a polymeric matrix and a nanoscaledispersed phase, the layer having a random anisotropic nanostructuredsurface, the random anisotropic nanostructured surface having an averagereflection at 60 degrees off angle less than 1 percent, the layer havinga thickness of at least 500 nm, and the layer having a visible lighttransmission through the thickness of the layer at 90 degrees to therandom anisotropic nanostructured surface of at least 94 percent, themethod comprising: providing the polymeric matrix comprising thenanodispersed phase; and etching at least a portion of the polymericmatrix using plasma to form the random nanostructured surface.
 3. Themethod of claim 1, wherein the nanoscale phase is present in a rangefrom 60 nm to 90 nm in size, in a range from 30 nm to 50 nm in size, andless than 25 nm in size, and wherein the nanoscale phase is present in arange from 0.25 wt. % to 50 wt. % for sizes in the range from 60 nm to90 nm, 1 wt. % to 50 wt. % for sizes in a range from for sizes in therange from 30 nm to 50 nm, and 0.25 wt. % to 25 wt. % for sizes lessthan 25 nm, based on the total weight of the polymeric matrix andnanoscale phase.
 4. The method of claim 1, wherein the nanoscale phaseis present in a range from 60 nm to 90 nm in size, in a range from 30 nmto 50 nm in size, and less than 25 nm in size, and wherein the nanoscalephase is present in the range from 0.1 vol. % to 35 vol. % for sizes inthe range from 60 nm to 90 nm, 0.1 vol. % to 25 vol. % for sizes in arange from 30 nm to 50 nm, and 0.1 vol. % to 10 vol. % for sizes lessthan 25 nm, based on the total volume of the polymeric matrix andnanoscale phase.
 5. The method of claim 1, wherein the nanoscale phasecomprises submicrometer particles.
 6. The method of claim 1, wherein thesubmicrometer particles are covalently bonded to the polymeric matrix.7. The method of claim 2, wherein the nanoscale phase is present in arange from 60 nm to 90 nm in size, in a range from 30 nm to 50 nm insize, and less than 25 nm in size, and wherein the nanoscale phase ispresent in a range from 0.25 wt. % to 50 wt. % for sizes in the rangefrom 60 nm to 90 nm, 1 wt. % to 50 wt. % for sizes in a range from forsizes in the range from 30 nm to 50 nm, and 0.25 wt. % to 25 wt. % forsizes less than 25 nm, based on the total weight of the polymeric matrixand nanoscale phase.
 8. The method of claim 2, wherein the nanoscalephase is present in a range from 60 nm to 90 nm in size, in a range from30 nm to 50 nm in size, and less than 25 nm in size, and wherein thenanoscale phase is present in the range from 0.1 vol. % to 35 vol. % forsizes in the range from 60 nm to 90 nm, 0.1 vol. % to 25 vol. % forsizes in a range from 30 nm to 50 nm, and 0.1 vol. % to 10 vol. % forsizes less than 25 nm, based on the total volume of the polymeric matrixand nanoscale phase.
 9. The method of claim 2, wherein the nanoscalephase comprises submicrometer particles.
 10. The method of claim 2,wherein the submicrometer particles are covalently bonded to thepolymeric matrix.